Angle Spinning Nuclear Magnetic Resonance Research Articles

Evolution of the Cellulose Microfibril through Gamma-Valerolactone-Assisted Co-Solvent and Enzymatic Hydrolysis

Biomass recalcitrance during deconstruction remains a key bottleneck to affordable biomass processing technologies. A clear connection between the cell wall structure and biomass deconstruction is necessary to understand how lignocellulosic material is broken down to valuable monomeric components. Here, we monitor changes in the cellulose microfibril domains of poplar, sorghum, and switchgrass throughout gamma-valerolactone (GVL)–water co-solvent pretreatment and enzymatic hydrolysis using solid-state 13C cross-polarization magic angle spinning nuclear magnetic resonance spectroscopy (CP/MAS 13C-NMR) and wide-angle X-ray scattering (WAXS). Spectral fitting of NMR peaks corresponding to different cellulose microenvironments at the C4 carbon center suggests that a mildly acidic GVL–water co-solvent pretreatment of poplar leads to nearly full removal of xylan–cellulose linkages, which primes the cellulose for enzymatic attack. The spectral fitting also suggests that the pretreatment causes significant depletion of the inaccessible fibril surface domains with an increase in more thermally stable crystalline resonances (Iβ). WAXS confirmed a decrease in the lattice spacing between (200) crystalline planes with increasing co-solvent pretreatment severity. These results are interpreted as an opening of bound microfibril surfaces previously inaccessible to the co-solvent system, which leaves behind a more thermally stable, crystalline domain that is potentially prone to relaxation and recrystallization. Full conversion of residual GVL-pretreated biomass was achieved after the GVL co-solvent pretreatment at 140 °C using a commercial enzyme cocktail, CTec2, which contains different cellulases and other enzymes. Spectral fitting of enzymatically hydrolyzed samples by a single engineered cellulase, CelR, suggests that the residual cellulose recalcitrance is mainly due to the inability of CelR to digest the Iβ crystalline domain present in pretreated samples. This work helps to provide new information regarding the structure of the cell wall and recalcitrance throughout GVL–water mild acidolysis and CelR enzymatic biomass deconstruction by tracking the evolution of structural domains within the cellulose microfibril. This work further directs recommendations for improving the conversion and sugar yields in future studies. Our findings inform inquiry into larger questions of cellulose recalcitrance through GVL pretreatment and CelR enzymatic hydrolysis and give insight into subsequent required steps for full cellulose conversion with attention to the most recalcitrant cellulose structures.

Pb2+ and Cr3+ immobilization efficiency and mechanism in red-mud-based geopolymer grouts

Herein, a green geopolymer composite was prepared using red mud and granulated blast furnace slag by immobilizing Pb2+ and Cr3+ to improve the utilization rate of red mud for heavy metal solidification and grouting engineering. The mechanical strength, leaching characteristics, and immobilization mechanisms of geopolymer grouts were investigated via Fourier transform infrared spectroscopy, X-ray diffraction, magic angle spinning–nuclear magnetic resonance spectroscopy, X-ray photoelectron spectroscopy, and scanning electron microscopy–energy-dispersive spectroscopy. Results demonstrate that the mechanical strength of the red-mud-based grout first increased and then decreased with an increasing alkali activator modulus. Moreover, red mud could participate in the geopolymerization reaction because of its aluminosilicate component. Furthermore, both Pb2+ and Cr3+ improved the mechanical strength of red-mud-based grouts at contents of 0.4 and 0.6 wt%, respectively. However, the mechanical strength drastically decreased when the dosages for both were 1.0 wt%. These chemical fractions of Pb2+ and Cr3+ evidence that the soluble and exchangeable fractions could be converted to a carbonate-bound fraction, iron–manganese oxide, and an organic fraction; however, the immobilization rates reached 91.46% and 95.86%, respectively. The characterization results confirm the participation of Pb2+ and Cr3+ in the geopolymerization, and Pb2+ and Cr3+ were immobilized by the chemical bonding and physical sealing effects.

Active Sites in H-Mordenite Catalysts Probed by NMR and FTIR

Mordenites are widely used in catalysis and environmental protection. The catalytic properties of mordenite are largely determined by the composition of its crystal framework, i.e., the SiO2/Al2O3 molar ratio (MR), and the cationic form. In H-mordenites, the most important characteristic becomes the structure and distribution of acid sites, which depends on the number and distribution of Al tetrahedra in the framework. In the present work, the local structure of these centers in H-mordenite catalysts with a nominal MR varied from 9.9 to 19.8 was studied in detail using a combination of magic angle spinning nuclear magnetic resonance (MAS NMR) and Fourier transform infrared spectroscopy (FTIR). 27Al MAS NMR indicates the presence of extra-framework Al in most of the studied samples that results in a higher real MR of the zeolitic framework compared to the nominal value. Concentrations of Lewis and Brønsted acid sites, as well as of silanol groups were estimated by elemental analysis, NMR, and FTIR spectroscopy. The values of site concentrations obtained from band intensities of adsorbed CO and those of OH groups are compared with the amount of framework and extra-framework aluminum. The advantages and restrictions of different methods of active site characterization are discussed.

Tribochemical synthesis of functionalized covalent organic frameworks for anti-wear and friction reduction

Tribochemistry can be defined as a field dealing with the chemical reactions occurring in the friction zone, capable of catalyzing mechanical and physico-chemical changes in the friction contact area, facilitating the formation of tribo-films, which is also an efficient approach to fabricate novel innovative materials. In this paper, we report the successful synthesis of the silicon oil (SO)-functionalized covalent organic frameworks (COFs) prepared via the tribochemical method when subjected to the reciprocating friction; during the friction process, the rich aldehyde-terminated COFs can bond with amino SO via the Schiff base reaction between aldehyde group and amino group to obtain the desired functionalized COFs (SO@COF-LZU1). The tribochemical reaction progress was tracked through in-situ monitoring of the friction coefficient and the operating conditions during the entire friction process. Noticeably, the friction coefficient continued to decrease until it finally stabilized as the reaction progressed, which revealed the formation of a protective tribo-film. Herein, an approximate tribochemical model was presented, wherein the reaction mechanism was investigated and analyzed by employing structural analysis techniques like magic angle spinning nuclear magnetic resonance (MAS NMR), transmission electron microscopy (TEM), and X-ray photoelectron spectroscopy (XPS). Furthermore, the tribochemical-induced SO@COF-LZU1 exhibited remarkable tribological performance with a low friction coefficient of 0.1 and 95.5% reduction in wear volume when used as additives of 500SN base oil. The prime focus of our research was on the preparation and functionalization of COF materials via tribochemical reactions, unraveling a new avenue for the rational design and preparation of functional materials.

Application of 1H HR-MAS NMR-Based Metabolite Fingerprinting of Marine Microalgae

Natural products from the marine environment as well as microalgae, have been known for the complexity of the metabolites they produce due to their adaptability to different environmental conditions, which has been an inexhaustible source of several bioactive properties, such as antioxidant, anti-tumor, and antimicrobial. This study aims to characterize the main metabolites of three species of microalgae (Nannochloropsis oceanica, Chaetoceros muelleri, and Conticribra weissflogii), which have important applications in the biofuel and nutrition industries, by 1H High-resolution magic angle spinning nuclear magnetic resonance (1H HR-MAS NMR), a method which is non-destructive, is highly reproducible, and requires minimal sample preparation. Even though the three species were found in the same ecosystem and a superior production of lipid compounds was observed, important differences were identified in relation to the production of specialized metabolites. These distinct properties favor the use of these compounds as leaders in the development of new bioactive compounds, especially against environmental, human, and animal pathogens (One Health), and demonstrate their potential in the development of alternatives for aquaculture.

Identifying the Point of Attachment in the Hypercrosslinking of Benzene for the Synthesis of a Nanoporous Polymer as a Superior Adsorbent for High-Pressure CO2 Capture Application

The point of attachment in the hypercrosslinking of benzene using formaldehyde dimethyl acetal as the crosslinker, anhydrous ferric chloride as the catalyst, and 1,2 dichloroethane as the solvent for the synthesis of poly-benz is reported. A fast microwave-assisted synthesis, within a reaction time of 60 min, resulted in the formation of nanoporous poly-benz having a specific surface area of 1168 m2 g–1. A thorough analysis of poly-benz using 13C cross-polarization magic angle spinning nuclear magnetic resonance and X-ray photoelectron spectra has revealed the hypercrosslinking at the meta position of the benzene ring. The synthesized poly-benz further shows a high CO2 capture capacity of 65.3 wt % at 298 K and 30 bar. Various adsorption isotherm models have been fitted at different temperatures up to 30 bar to represent the equilibrium CO2 adsorption data.

Monitoring of the conductivity properties with respect to the development of geopolymer network

In this work, we focused on the chemical and (micro)structural changes that occur during curing at different temperatures of geopolymers (GP) prepared with a mullite-based precursor obtained by sol-gel synthesis. Several factors, such as the Si-to-Al ratio in the precursors and the curing temperatures, affect geopolymerisation. While potassium, sodium and even lithium are the most commonly studied cations, for this study, we examined geopolymers with sodium cations only. The H2O:Na2O ratio was set high at 22.80 to allow good workability of the paste having in mind the intended thin film application, i.e. the water-to-geopolymer binder ratio was set at 0.64. We performed extensive structural (diffraction and vibrational spectroscopy), morphological (electron microscopy) and electrical (impedance spectroscopy) characterisation, to facilitate an understanding of the conditions behind the optimal geopolymerisation. Particular attention was paid to the study of the evolution of the GP system as a function of curing temperature using solid-state magic angle spinning nuclear magnetic resonance. This allowed us to better understand the influence of the chemical composition of the constituents and their homogeneity, on the evolution of the organizational domains and electrical properties of the GP samples. We have explored the feasibility of moving from a relatively porous bulk to a thin film configuration, highlighting the applicability of geopolymers as constituents in photovoltaic facade systems.

Effect of Different Initial CaO/SiO2 Molar Ratios and Curing Times on the Preparation and Formation Mechanism of Calcium Silicate Hydrate.

To better understand the pozzolanic activity in fly ash used as a supplementary cementitious material in cement or concrete, calcium silicate hydrate (C-S-H) has been synthesized by adding silica fume to a supersaturated calcium hydroxide solution prepared by mixing calcium oxide and ultrapure water. Thermogravimetric analysis results have revealed the variation in the weight loss due to C-S-H in the samples and the conversion ratio of calcium oxide (the μCaO value), which represents the proportion of calcium oxide in the initial reaction mixture used to produce C-S-H, with curing time. The weight loss due to C-S-H and the μCaO value were both maximized (13.5% and 90.4%, respectively) when the initial C/S molar ratio was 1.0 and the curing time was 90 d. X-ray diffraction (XRD) analysis has indicated that C-S-H in the samples after curing for 7 d had the composition Ca1.5SiO3.5·xH2O. 29Si magic angle spinning (MAS) nuclear magnetic resonance (NMR) analysis has revealed that the degree of polymerization of C-S-H increased with an increase in curing time for samples with an initial C/S molar ratio of 1.0. The ratio of internal to terminal tetrahedra (Q2/Q1) increased from 2.29 to 4.28 with the increase in curing time from 7 d to 90 d. At curing times ≥ 28 d, a leaf-like C-S-H structure was observed by scanning electron microscopy (SEM). An ectopic nucleation-polymerization reaction process is proposed for the formation mechanism of C-S-H.

Spectroscopic studies on phosphate-modified silicon oxycarbide-based amorphous materials

Vibrational spectroscopy is the most effective, efficient and informative method of structural analysis of amorphous materials with silica matrix and, therefore, an indispensable tool for examining silicon oxycarbide-based amorphous materials (SiOC). The subject of this work is a description of the modification process of SiOC glasses with phosphate ions based on the structural examination including mainly Infrared and Raman Spectroscopy. They were obtained as polymer-derived ceramics based on ladder-like silsesquioxanes synthesised via the sol-gel method. With the high phosphate’s volatility, it was decided to introduce the co-doping ions to create [AlPO4] and [BPO4] stable structural units. As a result, several samples from the SiPOC, SiPAlOC and SiPBOC systems were obtained with various quantities of the modifiers. All samples underwent a detailed structural evaluation of both polymer precursors and ceramics after high-temperature treatment with Fourier-transformed infrared spectroscopy (FTIR), Raman spectroscopy, X-ray diffraction (XRD) and magic angle spinning nuclear magnetic resonance (MAS-NMR). Obtained results proved the efficient preparation of desired materials that exhibit structural parameters similar to the unmodified one. They were X-ray-amorphous with no phase separation and crystallisation. Spectroscopic measurements confirmed the presence of the crucial Si-C bond and how modifying ions are incorporated into the SiOC network. It was also possible to characterise the turbostratic free carbon phase. The modification was aimed to improve the bioperformance of the materials in the context of their future application as bioactive coatings on metallic implants.

HRMAS-NMR and simulation study of the self-assembly of surfactants on carbon nanotubes.

Polyethoxylated surfactants, such as those of the Tween and Pluronic series, are commonly used to disperse carbon nanotubes (CNTs) and other nanoparticles. However, the current understanding of the nature of interactions between these surfactants and CNTs is limited. The nature of the interactions between surfactants (Tween-80 [T80] and Pluronic F68 [PF68]) and CNTs was investigated using high-resolution magic angle spinning nuclear magnetic resonance (HRMAS-NMR) and coarse-grained molecular dynamics (MD) simulations. HRMAS-NMR revealed that T80 molecules interact with single-walled CNTs (SWCNTs) and multi-walled CNTs (MWCNTs) via the oleyl chain, whereas PF68 molecules interact with the surface of SWCNTs and MWCNTs via the polypropylene oxide residues. The polyethylene oxide chains were oriented towards the external aqueous environment. The HRMAS-NMR results were supported by MD simulations, and the latter provided further insights into the nature of the interactions.

Highly porous phosphate-based glasses for controlled delivery of antibacterial Cu ions prepared via sol-gel chemistry.

Mesoporous glasses are a promising class of bioresorbable biomaterials characterized by high surface area and extended porosity in the range of 2 to 50 nm. These peculiar properties make them ideal materials for the controlled release of therapeutic ions and molecules. Whilst mesoporous silicate-based glasses (MSG) have been widely investigated, much less work has been done on mesoporous phosphate-based glasses (MPG). In the present study, MPG in the P2O5-CaO-Na2O system, undoped and doped with 1, 3, and 5 mol% of Cu ions were synthesized via a combination of the sol-gel method and supramolecular templating. The non-ionic triblock copolymer Pluronic P123 was used as a templating agent. The porous structure was studied via a combination of Scanning Electron Microscopy (SEM), Small-Angle X-ray Scattering (SAXS), and N2 adsorption-desorption analysis at 77 K. The structure of the phosphate network was investigated via solid state 31P Magic Angle Spinning Nuclear Magnetic Resonance (31P MAS-NMR) and Fourier Transform Infrared (FTIR) spectroscopy. Degradation studies, performed in water via Inductively Coupled Plasma-Optical Emission Spectroscopy (ICP-OES), showed that phosphates, Ca2+, Na+ and Cu ions are released in a controlled manner over a 7 days period. The controlled release of Cu, proportional to the copper loading, imbues antibacterial properties to MPG. A significant statistical reduction of Staphylococcus aureus (S. aureus) and Escherichia coli (E. coli) bacterial viability was observed over a 3 days period. E. coli appeared to be more resistant than S. aureus to the antibacterial effect of copper. This study shows that copper doped MPG have great potential as bioresorbable materials for controlled delivery of antibacterial ions.

Quantitative study on the dielectric properties of tricalcium silicate pastes under different W/C

C3S (tricalcium silicate) pastes with water-cement ratio (W/C) of 0.23, 0.3, 0.4 and 0.5 were designed, and the influence of the dielectric properties of C3S paste were quantitatively analyzed. The results show that when the W/C is 0.23, the real part of permitivity of the C3S paste is the smallest. With increases of the W/C, the real part of permitivity of the C3S paste decrease, and the loss tangent increases. The real part of permitivity of C3S paste decreases with the increase of Ca(OH)2 and pore phases, and increases with the increase of C3S and CSH gel phase. The permitivity of C3S paste decreases most due to increase pore phase (about 4 times that of Ca(OH)2 phase), and increases most due to increase CSH gel phase (about 6.6 times that of C3S phase). The dielectric weight coefficient proposed in this study can well predict the changing trend of the real part of permitivity of C3S pastes with different W/C. Finally, based on the Thermogravimetric analysis (TGA), Scanning electron microscope (SEM), Mercury intrusion porosimetry (MIP), N2 adsorption and 29Si magic angle spinning nuclear magnetic resonance (29Si NMR) test results, the reasons of electromagnetic loss changes of C3S pastes with different W/C were analyzed from the molecular structure of CSH gel, the crystalline products and the pore structure of C3S paste.

Nanoscale Mg-Depleted Layers Slow Carbonation of Forsterite (Mg2SiO4) When Water Is Limited

Passivation of silicate surfaces by accumulated reaction products is an obstacle to efficient CO2 mineralization. In this study, we investigate a unique passivation effect during the carbonation of the basalt mineral forsterite (Mg2SiO4) in humid supercritical CO2 (50 °C, 90 bar). Using in situ high-pressure infrared spectroscopy, we demonstrate that dissolution of forsterite into a thin water film slows significantly after reaction for ≈24 h, even under far-from-equilibrium conditions. 29Si magic angle spinning nuclear magnetic resonance spectroscopy detects a highly polymerized amorphous silica at this stage. On the basis of transmission electron microscopy and energy dispersive X-ray spectroscopy, we show that the silica is present as a Mg-depleted layer that is just 2–3 nm thick on the reacted forsterite particles. The decrease in the level of forsterite dissolution in the presence of an extraordinarily thin Mg-depleted layer can be strongly linked to properties of the thin fluid film at the surface, highlighting the importance of water during mineral carbonation. This study furthers our understanding of silicate mineral carbonation under select low-water, humidified fluid conditions relevant to basaltic geologic reservoirs, recovery of critical elements by carbonation of mafic ores, and sequestration of atmospheric CO2 by enhanced rock weathering.

Electrochemical and spectroscopic studies on carbon‐coated and iodine‐doped LiFeBO3 as a cathode material for lithium‐ion batteries

AbstractIn this study, monoclinic LiFeBO3 was carbon‐coated and iodine doped via a solid‐state reaction to improve the electrochemical performance of pristine LiFeBO3 as cathode material in lithium‐ion batteries. In order to enhance the electrical conductivity of LiFeBO3, the highly electronegative iodide anion was doped in a limited amount (x = 0.005) at the oxygen site of the borate to produce LiFeBO3−xI2x. A thin carbon layer was then deposited in situ on the LiFeBO2.995I0.01 particles (to produce “LFBI/C”) to protect them from air and moisture. Field‐emission scanning electron microscopy (FE‐SEM) data indicated the aggregated morphology of the synthesized samples. Powder X‐ray diffraction (XRD) and 7Li magic angle spinning (MAS) nuclear magnetic resonance (NMR) measurements revealed that both the doped and undoped LiFeBO3‐based samples had mainly monoclinic structures, although a small amount of a vonsenite‐type phase was formed upon iodine doping. X‐ray photoelectron spectroscopy (XPS) and energy dispersive X‐ray spectroscopy (EDX) data confirmed the successful insertion of iodine in the cathode material. The specific discharge capacity of LFBI/C at 0.05 C rate (144.68 mAh g−1) was higher than that of carbon‐coated LiFeBO3 (122.46 mAh g−1). The increased capacity of LFBI/C was also evident in long charge–discharge cycles conducted at 1 C rate and in the overall rate performance. Interestingly, the iodine‐doped sample exhibited significantly high specific discharge capacity even at 10 C rate.

Aluminosilicate-Supported Catalysts for the Synthesis of Cyclic Carbonates by Reaction of CO2 with the Corresponding Epoxides.

Functionalized aluminosilicate materials were studied as catalysts for the conversion of different cyclic carbonates to the corresponding epoxides by the addition of CO2. Aluminum was incorporated in the mesostructured SBA-15 silica network. Thereafter, functionalization with imidazolium chloride or magnesium oxide was performed on the Al_SBA-15 supports. The isomorphic substitution of Si with Al and the resulting acidity of the supports were investigated via 27Al magic angle spinning (MAS) nuclear magnetic resonance (NMR) spectroscopy and NH3 adsorption microcalorimetry. The Al content and the amount of MgO were quantified via inductively coupled plasma optical emission spectroscopy (ICP-OES) analysis. The anchoring of the imidazolium salt was assessed by 29Si and 13C MAS NMR spectroscopy and quantified by combustion chemical analysis. Textural and structural properties of supports and catalysts were studied by N2 physisorption and X-ray diffraction (XRD). The functionalized systems were then tested as catalysts for the conversion of CO2 and epoxides to cyclic carbonates in a batch reactor at 100 or 125 °C, with an initial CO2 pressure (at room temperature) of 25 bar. Whereas the activity of the MgO/xAl_SBA-15 systems was moderate for the conversion of glycidol to the corresponding cyclic carbonate, the Al_SBA-15-supported imidazolium chloride catalysts gave excellent results over different epoxides (conversion of glycidol, epichlorohydrin, and styrene oxide up to 89%, 78%, and 18%, respectively). Reusability tests were also performed. Even when some deactivation from one run to the other was observed, a comparison with the literature showed the Al-containing imidazolium systems to be promising catalysts. The fully heterogeneous nature of the present catalysts, where the inorganic support on which the imidazolium species are immobilized also contains the Lewis acid sites, gives them a further advantage with respect to most of the catalytic systems reported in the literature so far.

Designing a quality assurance process for quality control of nuclear magnetic resonance metabolomics studies of human blood.

High-resolution magic angle spinning (HRMAS) nuclear magnetic resonance (NMR)-based metabolomics has demonstrated its utility in studies of biofluids for various diseases. HRMAS NMR spectroscopy is uniquely well suited for analyzing human blood samples because of the small quantity of samples and minimal preparation required. To develop this methodology into standardized clinical protocols, establishment of the method's quality assurance (QA) and evaluations of its quality control (QC) are critical. This study aims to assess the QA/QC measured from human blood specimens in the form of serum and plasma through within-subject and between-subject comparisons, as well as stability and consistency comparisons over several freezing-thawing cycles of sample storage conditions, and most importantly, the agreement of pooled control samples against individual samples.

Interlayer Cation Polarizability Affects Supercritical Carbon Dioxide Adsorption by Swelling Clays.

Several strategies for mitigating the build-up of atmospheric carbon dioxide (CO2) bring wet supercritical CO2 (scCO2) in contact with phyllosilicates such as illites and smectites. While some work has examined the role of the charge-balancing cation and smectite framework features on CO2/smectite interactions, to our knowledge no one has examined how the polarizability of the charge-balancing cation influences these behaviors. In this paper, the scCO2 adsorption properties of Pb2+, Rb+, and NH4+ saturated smectite clays at variable relative humidity are studied by integrating in situ high-pressure X-ray diffraction (XRD), infrared spectroscopic titrations, and magic angle spinning nuclear magnetic resonance (MAS NMR) methods. The results are combined with previously published data for Na+, Cs+, and Ca2+ saturated versions of the same smectites to isolate the roles of the charge-balancing cations and perform two independent tests of the role of charge-balancing cation polarizability in determining the interlayer fluid properties and smectite expansion. Independent correlations developed for (i) San Bernardino hectorite (SHCa-1) and (ii) Wyoming montmorillonite (SWy-2) both show that cation polarizability is important in predicting the interlayer composition (mol% CO2 in the interlayer fluid and CO2/cation ratio in interlayer) and the expansion behavior for smectites in contact with wet and dry scCO2. In particular, this study shows that the charge-balancing cation polarizability is the most important cation-associated parameter in determining the expansion of the trioctahedral smectite, hectorite, when in contact with dry scCO2. While both independent tests show that cation polarizability is an important factor in smectite-scCO2 systems, the correlations for hectorite are different from those determined for montmorillonite. The root of these differences is likely associated with the roles of the smectite framework on adsorption, warranting follow-up studies with a larger number of unique smectite frameworks. Overall, the results show that the polarizability of the charge-balancing cation should be considered when preparing smectite clays (or industrial processes involving smectites) to capture CO2 and in predicting the behavior of caprocks over time.

Doping engineering of scandium‐based solid‐state electrolytes toward superior ionic conductivity

AbstractOne key research point of solid‐state electrolytes (SSEs) is ionic conductivity. To date, their ionic conductivity is relatively low to meet the requirements of practical applications; thus, more investigations on the migration mechanisms are needed. Here, we constructed scandium‐based halide SSEs (Li3‐xSc1‐x(Zr/Hf)xCl6, x = 0 ~ 0.5). The highest ionic conductivities (1.61 and 1.33 mS/cm) and the lowest activation energies (0.326 and 0.323 eV) are shown in Li2.6Sc0.6Zr0.4Cl6 (LSZC~0.4) and Li2.6Sc0.6Hf0.4Cl6 (LSHC~0.4), respectively. Their electrochemical windows in the cells of Li/Li7P3S11/LSZC~0.4/LSZC~0.4‐C and Li/Li7P3S11/LSHC~0.4/LSHC~0.4‐C are 1.3 ~ 4.2 V and 1.6 ~ 4.1 V versus Li+/Li, respectively. The crystal structures and the Li+ chemical environments were investigated by X‐ray diffraction and 7Li solid‐state magic angle spinning nuclear magnetic resonance, indicating weaker bond strengths of LiCl to facilitate the transportation of Li+. The potential reason explaining the increased ionic conductivity was determined based on the bond valence site energy theory.image

Highly selective epoxidation of styrene at ambient temperature under photo-assisted condition over bimetallic Eu and Ti-doped amino-functionalized mesoporous molecular sieve

Mesoporous molecular sieves silica materials had been functionalized employing 3-aminopropyltriethoxysilane as the surface decoration agent by a post-synthesis method and Eu and Ti with different loading ratio were synchronously anchored on amino-functionalized silica framework by incipient wetness impregnation method, respectively. The structures of the synthesized samples were evaluated by means of X-ray diffraction, Fourier transform infrared spectroscopy, ultraviolet-visible spectra, scanning electron microscope, transmission electron microscope, X-ray photoelectron spectroscopy and solid-state 29Si magic angle spinning nuclear magnetic resonance spectra. The results revealed that the highly ordered mesoporous two dimensional hexagonal structure and the mesoporous channel structure were well preserved and isolated tetrahedral surface Eu3+ and isolated [TiO4] or [HOTiO3] species were found to be grafted and highly dispersed in the amino-functionalized mesoporous framework. A significant enhancement in selectivity and conversion for the photocatalytic epoxidation of styrene has been achieved by synergistic effect based on surface ligand effect and electron density effect between Eu3+ and Ti4+ species on amino-functionalized mesoporous silica framework. The factors associated with the conversion of styrene and selectivity to styrene oxide such as the solvent, metal loading, the amount of NaOH, H2O2/Styrene, the amount of catalyst and reaction time were also investigated in details. The desired selectivity (84%) to styrene oxide and excellent conversion (32%) of styrene for the photocatalytic epoxidation of styrene with turnover frequency of 3.1 × 10−4s−1 were obtained using aqueous H2O2 as an oxidant in the presence of acetonitrile solvent under ambient temperature.

Understanding the Capacity Decay of Si/NMC622 Li-Ion Batteries Cycled in Superconcentrated Ionic Liquid Electrolytes: A New Perspective.

Silicon-containing Li-ion batteries have been the focus of many energy storage research efforts because of the promise of high energy density. Depending on the system, silicon generally demonstrates stable performance in half-cells, which is often attributed to the unlimited lithium supply from the lithium (Li) metal counter electrode. Here, the electrochemical performance of silicon with a high voltage NMC622 cathode was investigated in superconcentrated phosphonium-based ionic liquid (IL) electrolytes. As a matter of fact, there is very limited work and understanding of the full cell cycling of silicon in such a new class of electrolytes. The electrochemical behavior of silicon in the various IL electrolytes shows a gradual and steeper capacity decay, compared to what we previously reported in half-cells. This behavior is linked to a different evolution of the silicon morphology upon cycling, and the characterization of cycled electrodes points toward mechanical reasons, complete disconnection of part of the electrode, or internal mechanical stress, due to silicon and Li metal volume variation upon cycling, to explain the progressive capacity fading in full cell configuration. An extremely stable solid electrolyte interphase (SEI) in the full Li-ion cells can be seen from a combination of qualitative and quantitative information from transmission electron microscopy, X-ray photoelectron spectroscopy, electrochemical impedance spectroscopy, and magic angle spinning nuclear magnetic resonance. Our findings provide a new perspective to full cell interpretation regarding capacity fading, which is oftentimes linked almost exclusively to the loss of Li inventory but also more broadly, and provide new insights into the impact of the evolution of silicon morphology on the electrochemical behavior.